Sunscreen compositions as well as dihydropyridines and dihydropyranes

ABSTRACT

1,4-dihydropyridine and 1,4-dihydropyrane derivatives and novel cosmetic or dematological sunscreen compositions containing novel and/or known 1,4-dihydropyridine or 1,4-dihydropyrane derivatives which are useful for photoprotecting human skin and/or hair against UV radiation, in particular solar radiation, and the use of such 1,4-dihydropyridine and/or 1,4-dihydropyrane derivatives as UV-A screening agents, particularly in cosmetic and pharmaceutical compositions.

The present invention relates to novel 1,4-dihydropyridine and1,4-dihydropyrane derivatives, to novel cosmetic or dermatologicalsunscreen compositions containing certain novel and/or known1,4-dihydropyridine or 1,4-dihydropyrane derivatives which are usefulfor photoprotecting human skin and/or hair against UV radiation, inparticular solar radiation, and to the use of such 1,4-dihydropyridineand/or 1,4-dihydropyrane derivatives as UV-A screening agents,particularly in cosmetic and pharmaceutical compositions.

More particularly, in one aspect the invention relates to novel cosmeticor dermatological sunscreen compositions comprising a1,4-dihydropyridine derivative of the general formula I or a1,4-dihydropyrane derivative of the general formula II

wherein

-   -   m is 1 or 2;    -   R¹ and R² are identical or different electron-withdrawing        groups, or one of R¹ and R² is hydrogen and the other of R¹ and        R² is an electron-withdrawing group;    -   R³, R⁴, R⁵, are R⁶ are, independently, hydrogen, alkyl,        cycloalkyl or aryl;    -   R³ and R⁵ and/or R⁴, and R⁶ taken together with the carbon atoms        to which they are attached, may form a 5 or 6 membered ring        which optionally is substituted with one to four alkyl,        cycloalkyl or alkoxy groups;    -   X is a moiety R⁷, when m is 1; and is alkylene or        poly(oxyalkylene) when m is 2; and    -   R⁷ is hydrogen, alkyl, cycloalkyl, alkoxyalkyl or aryl.

As used herein the term “electron-withdrawing groups” refers to groupscontaining a multiple bond such as a nitrilo (—CN) group or a —COOR⁸,—COR⁸ or —CONR⁸ group, wherein R⁸ is hydrogen, alkyl, cycloalkyl oraryl. Alkyl, alone and in combination with alkoxy refers to saturatedstraight or branched chain hydrocarbon groups containing 1 to 21,preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl,isopropyl, butyl, sec. butyl, isobutyl, pentyl, neopentyl, hexyl,2-ethyl-hexyl, and octyl. Alkoxy, alone and in combination with alkylrefers to alkyl groups as defined above which are bound through anoxygen.

Aryl refers to aromatic, optionally substituted hydrocarbon groups suchphenyl or phenyl groups substituted by one to three alkyl of 1 to 6carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atomsor by a mixture thereof, or naphthyl residues.

Alkoxyalkyl refers to alkyl groups as defined earlier which areinterrupted by an oxygen atom, such as methoxymethyl, methoxyethyl,ethoxyethyl, 3-(2-ethylhexyloxy)propyl etc.

Alkylene refers to alkyl groups as defined above which have anadditional free valence bond, such as methylene, ethylene,1,3-propylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene,and 1,8-octylene.

The term poly(oxyalkylene) as used herein denotes a compound containinga polyether backbone. The polyether backbone can be based e.g. onpropyleneoxide (PO), ethylene-oxide (EO) or mixed EO/PO. Examples ofpoly(oxyalkylene) are —(R⁹—O—R¹⁰)_(x)—O—(R¹¹—O—R¹²)_(y)—, wherein R⁹,R¹⁰, R¹¹ and R¹² are, independently, methylene, ethylene, propylene orisopropylene, and x and y are, independently 1,2 or 3.

The compounds of the general formulas I and II above can be preparedaccording to procedures known in the art. Preferably, the compounds ofthe general formula I and II can be prepared by reacting a compound ofthe general formula III

-   -   wherein R¹ through R⁶ have the meanings given earlier,    -   with a compound of the general formula IV        R¹—CH₂—R²  (IV)    -   wherein R¹ and R² have the meanings given earlier, to yield a        compound of the general formula II and, if required, reacting        the compound of the formula II with a compound of the general        formula V        R⁷—NH₂  (V)    -   wherein R⁷ has the meanings given earlier,    -   to yield a compound of the general formula I wherein m is 1 and        X is R⁷;    -   or with an α,ω-diamino-alkane, or with an        α,ω-diamino-poly(oxyalkylene), e.g., a compound of the general        formula VI        H₂N—(R⁹—O—R¹⁰)_(x)—O—(R¹¹—O—R¹²)_(y)—NH₂  (VI)    -   wherein R⁹, R¹⁰, R¹¹,R¹², x and y are as defined earlier,    -   to yield a compound of the general formula I wherein m is 2 and        X is alkylene or poly(oxyalkylene).

The condensation of a compound of formula III with a compound of formulaIV can be accomplished by reacting the compounds in acetic anhydride atelevated temperature such as heating to reflux and work-up of thereaction mixture by removal of the acetic anhydride, extraction of theresidue with ether and chromatography. The compound of formula II can beconverted into a compound of the formula I by reaction with theappropriate amine V or VI at elevated temperature, e.g. at refluxtemperature of the reaction mixture. The starting compounds of formulaIII, V and VI are known or belong to a class of known compounds and canbe prepared by methods known per se and/or described hereinafter.

The above formulae I and II encompass novel compounds which, as such,are also an object of the present invention. The novel compounds includecompounds of formulae I and II wherein R³ and R⁴ are alkyl, or whereinR³ and R⁵ and/or R⁴, and R⁶ taken together with the carbon atoms towhich they are attached, form a 5 or 6 membered ring which optionally issubstituted with one to four alkyl or alkoxy groups; and compounds offormula I, wherein m is 2.

In formula I the following significances are preferred independently,collectively or in any combination or sub-combination:

-   -   (a) R¹ and R² are, independently, a group —CN, COOR⁸, COR⁸ or        CONR⁸ wherein R⁸ is hydrogen, alkyl, cycloalkyl or aryl; e.g. R¹        and R² are a group —CN or R¹ is a group —CN and R² is a group        COOR⁸.    -   (b) m is 1 or 2.    -   (c) R³ and R⁴ are hydrogen and R⁵ and R⁶ are alkyl or        cycloalkyl.    -   (d) R⁷ is alkyl, cycloalkyl or alkoxyalkyl.    -   (e) R² is a group COOR⁸ and R⁸ is alkyl.    -   (f) X is a group —(R⁹—O—R¹⁰)_(x)—O—(R¹¹—O—R¹²)_(y)—, wherein R⁹,        R¹⁰, R¹¹ and R¹² are, independently, methylene, ethylene or        propylene, and x and y are, independently 1,2 or 3.

In formula II the following significances are preferred independently,collectively or in any combination or sub-combination:

-   -   (a) R¹ and R² are, independently, a group —CN, COOR⁸, COR⁸ or        CONR⁸, e.g. R¹ and R² are a group —CN or R¹ is a group —CN and        R² is a group COOR⁸.    -   (b) R³ and R⁴ are hydrogen and R⁵ and R⁶ are alkyl or        cycloalkyl.    -   (c) R³, R⁴, R⁵ and R⁶ are alkyl or cycloalkyl.

Preferred compounds for use in the present invention are compounds ofthe formula I. From the compounds of the formula I, those wherein m is 1and both R¹ and R² are a group —CN, or R¹ is a group —CN and R² is agroup COOR⁸, R³ and R⁴ are hydrogen, R⁵ and R⁶ are alkyl, and R⁷ isalkyl or alkoxyalkyl are preferred. R⁸ is preferably alkyl. From thecompounds of the formula I, wherein m is 2 those, are preferred whereinR¹ and R² are a group —CN, and, further, X is—(R⁹—O—R¹⁰)_(x)—O—(R¹¹—O—R¹²)_(y)—, wherein R⁹, R¹⁰, R¹¹ and R¹², x andy are as defined earlier.

Specifically, novel compounds included within the scope of the presentinvention are

-   2-{1-[3-(2-{2-[3-(4-dicyanomethylene-2,6-dimethyl-4H-pyridin-1-yl)-propoxy]-ethoxy}-ethoxy)-propyl]-2,6-dimethyl-1H-pyridin-4-ylidene}-malononitrile,-   1-N-(2-ethylhexyl)-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,-   1-N-dodecyl-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,-   1-N-[3-(2-ethylhexyloxy)propyl]-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,-   1-N-[3,5,5-trimethylhexyl]-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,-   2-ethylhexyl    (1-N-[3-(2-Ethylhexyloxy)propyl]-2,6-dimethyl-1H-pyridin-4-ylidene)cyanoacetate,-   2-ethylhexyl (2,6-dimethylpyran-4-ylidene)cyanoacetate,-   2-(2,6-diethyl-3,5-dimethylpyran-4-ylidene)malononitrile, and-   2-(3,5-diethyl-2,6-dipropylpyran-4-ylidene)malononitrile.

The present invention also relates to compositions comprising a compoundof formula I or II, formulated into a suitable support or substrate.Typically, the compositions of the invention are adopted for protectinga material that is sensitive to ultraviolet radiation, in particularsolar radiation, and comprises an effective photoprotective amount of atleast one of the compounds of formula I or II. In one preferredembodiment of the invention such compositions are suited for protectingthe skin and/or hair against the deleterious effects of UV-radiation. Inthis case, the compositions according to the invention are cosmeticcompositions which comprise a topically applicable,cosmetically-acceptable vehicle, diluent as carrier. According toanother embodiment of the invention, the compounds of formula I or IIcan be incorporated into a plastic substrate. Compounds I and/or II mayalso be used to stabilize photosensitive ingredients in topicalformulations particulary colorants, such as FD&C and D&C colorants,curcumin, riboflavin, lactoflavine, tartrazine, chinolinyellow,cochenille, azorubin, amaranth, ponceau 4R, erythrosin, indigotin,chlorophylle, chlorophyllin, caramel, Carbo medicinalis, carotinoids,bixin, norbixin, annato, orlean, capsanthin, capsorubin, lycopin,xanthophylle, flavoxanthin, lutein, kryptoaxanthin, rubixanthin,violaxanthin, rhodoxanthin, canthaxanthin, betanin, anthocyans, vitaminssuch as vitamin A, vitamin K1, vitamin C or other active ingredients.

The compounds of formula I and II have adsorption maxima in the UV-Aregion. For the preparation of light screening agents, especially ofpreparations for dermatological and/or cosmetic use, such as skinprotection and sunscreen formulations for everyday cosmetics a compoundof formula I or II may be incorporated in auxiliary agents, e.g. acosmetic base, which are conventionally used for such formulations.Where convenient, other conventional UV-A and/or UV-B screening agents,preferably a pigment, may also be added. The combination of UV filtersmay show a synergistic effect. The preparation of said light screeningagents is well known to the skilled artisan in this field. Theconcentration of UV filters is varied in a wide range. For example, theamount of compounds of formula I or II and optionally an additionalhydrophilic and/or lipophilic UV-A or UV-B screening agent other thanthe compounds of formula I or II may be in the range of from 0.5 to 12%by weight of the total composition. These additional screening agentsare advantageously selected from the compounds listed below withoutbeing limited thereto:

Examples of UV B screening agents, i.e. substances having absorptionmaxima between about 290 and 320 nm, which come into consideration forcombination with the compounds of the present invention are, e.g., thefollowing organic and inorganic compounds:

-   acrylates such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate    (octocrylene, PARSOL® 340), ethyl 2-cyano-3,3-diphenylacrylate and    the like;-   camphor derivatives such as 4-methyl benzylidene camphor (PARSOL®    5000), 3-benzyl-idene camphor, camphor benzalkonium methosulfate,    polyacrylamidomethyl benzyl-idene camphor, sulfobenzylidene camphor,    sulfomethyl benzylidene camphor, therephthalidene dicamphor sulfonic    acid and the like;-   cinnamate derivatives such as octyl methoxycinnamate (PARSOL® MCX),    ethoxyethyl methoxycinnamate, diethanolamine methoxycinnamate    (PARSOL® Hydro), isoamyl methoxycinnamate and the like as well as    cinnamic acid derivatives bond to siloxanes;-   p-aminobenzoic acid derivatives, such as p-aminobenzoic acid,    2-ethylhexyl p-dimethyl-aminobenzoate, N-oxypropylenated ethyl    p-aminobenzoate, glyceryl p-amino-benzoate,-   benzophenones such as benzophenone-3,    benzophenone-4,2,2′,4,4′-tetrahydroxy-benzophenone,    2,2′-dihydroxy-4,4′-dimethoxybenzophenone and the like;-   esters of benzalmalonic acid such as di(2-ethylhexyl)    4-methoxybenzalmalonate;-   esters of 2-(4-ethoxy anilinomethylene)propanedioic acid such as    2-(4-ethoxy anilinomethylene)propanedioic acid diethyl ester as    described in EP 895,776;-   organosiloxane compounds containing benzmalonate groups as described    in EP 358,584, EP 538,431 and EP 709,080;-   drometrizole trisiloxane (MEXORYL XL);-   pigments such as microparticulated TiO₂, and the like, wherein the    term “microparticulated” refers to a particle size from about 5 nm    to about 200 nm, particularly from about 15 nm to about 100 nm, and    which TiO₂ particles may be coated by metal oxides such as e.g.    aluminum or zirconium oxides or by organic coatings such as e.g.    polyols, methicones, aluminum stearate, alkyl silane;-   imidazole derivatives such as e.g. 2-phenyl benzimidazole sulfonic    acid and its salts (PARSOL® HS). Salts of 2-phenyl benzimidazole    sulfonic acid are e.g. alkali salts such as sodium- or potassium    salts, ammonium salts, morpholine salts, salts of primary, sec. and    tert. amines like monoethanolamine salts, diethanolamine salts and    the like;-   salicylate derivatives such as isopropylbenzyl salicylate, benzyl    salicylate, butyl salicylate, octyl salicylate (NEO HELIOPAN OS),    isooctyl salicylate or homomenthyl salicylate (homosalate, HELIOPAN)    and the like;-   triazine derivatives such as octyl triazone (UVINUL T-150), dioctyl    butamido triazone (UVASORB HEB), bis ethoxyphenol methoxyphenyl    triazine (TINOSORB S) and the like;-   encapsulated 2-ethylhexyl-4-methoxy cinnamate such as Eusolex®    UV-pearls™ OMC and the like.

Examples of UV A screening agents i.e. substances having absorptionmaxima between about 320 and 400 nm, which come into consideration forcombination with the compounds of the present invention are, e.g., thefollowing organic and inorganic compounds:

-   dibenzoylmethane derivatives such as 4-tert.    butyl-4′-methoxydibenzoyl-methane (PARSOL® 1789),    dimethoxydibenzoylmethane, isopropyldibenzoylmethane and the like;-   benzotriazole derivatives such as    2,2′-methylene-bis-(6-(2H-benzotriazole-2-yl)-4-(1,1,3,3,-tetramethylbutyl)-phenol    (TINOSORB M) and the like;-   phenylene-1,4-bis-benzimidazolsulfonic acids or salts such as    2,2-(1,4-phenylene)bis-(1H-benzimidazol-4,6-disulfonic acid)    (NEOHELIOPAN AP);-   amino substituted hydroxybenzophenones such as    2-(4-diethylamino-2-hydroxy-benzoyl)-benzoic acid hexylester as    described in EP 1,046,391;-   pigments such as microparticulated ZnO and the like, wherein the    term “microparticulated” refers to a particle size from about 5 nm    to about 200 nm, particularly from about 15 nm to about 100 nm, and    which ZnO particles may be coated by metal oxides such as e.g.    aluminum or zirconium oxides or by organic coatings such as e.g.    polyols, methicones, aluminum stearate, alkyl silane.

As dibenzoylmethane derivatives have limited photostability it may bedesirable to photostabilize these UV-A screening agents. Thus, the term“conventional UV-A screening agent” also refers to dibenzoylmethanederivatives such as e.g. PARSOL® 1789 stabilized by, e.g.,

-   3,3-diphenylacrylate derivatives as described in EP 514,491 and EP    780,119;-   benzylidene camphor derivatives as described in U.S. Pat. No.    5,605,680;-   organosiloxanes containing benzmalonate groups as described in EP    358,584, EP 538,431 and EP 709,080.

The compositions of the invention may also contain usual cosmeticadjuvants and additives, such as preservatives/antioxidants, fattysubstances/oils, water, organic solvents, silicones, thickeners,softeners, emulsifiers, additional sunscreens, antifoaming agents,moisturizers, fragrances, surfactants, fillers, sequestering agents,anionic, cationic, nonionic or amphoteric polymers or mixtures thereof,propellants, acidifying or basifyng agents, dyes, colorants, pigments ornanopigments, in particular those suited for providing an additionalphotoprotective effect by physically blocking out ultraviolet radiation,or any other ingredients usually formulated into cosmetics, inparticular for the production of sunscreen/antisun compositions. Thenecessary amounts of the cosmetic and dermatological adjuvants andadditives may, based on the desired product, easily be chosen by askilled artisan in this field and will be illustrated in the examples,without being limited hereto.

An additional amount of antioxidants/preservatives is generallypreferred. All known antioxidants usually formulated into cosmetics maybe used. Especially preferred are antioxidants chosen from the groupconsisting of amino acids (e.g. glycine, histidine, tyrosine,tryptophane) and their derivatives, imidazole (e.g urocanic acid) andderivatives, peptides such as D,L-carnosine, D-carnosine, L-carnosineand derivatives (e.g. anserine), carotinoids, carotenes (e.g.α-carotene, β-carotene, lycopene) and derivatives, chlorogenic acid andderivatives, liponic acid and derivatives (e.g. dihydroliponic acid),aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxine,glutathione, cysteine, cystine, cystamine and its glycosyl-, N-acetyl-,methyl-, ethyl-, propyl-, amyl-, butyl- and lauryl-, palmitoyl-; oleyl-,y-linoleyl-, cholesteryl- and glycerylester) and the salts thereof,dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionicacid and its derivatives (ester, ether, peptides, lipids, nucleotides,nucleosides and salts) as well as sulfoximine compounds (such asbuthionine sulfoximine, homocysteine sulfoximine, buthionine sulfone,penta-, hexa-, heptathionine sulfoximine) in very low compatible doses(e.g. pmol/kg to μmol/kg), additionally (metal)-chelators (such asα-hydroxyfatty acids, palmic-, phytinic acid, lactoferrin),α-hydroxyacids (such as citric acid, lactic acid, malic acid), huminicacid, gallic acid, gallic extracts, bilirubin, biliverdin, EDTA, EGTAand its derivatives, unsaturated fatty acids and their derivatives (suchas γ-linoleic acid, linolic acid, oleic acid), folic acid and itsderivatives, ubiquinone and ubiquinol and their derivatives, vitamine Cand derivatives (such as ascorbyl palmitate and ascorbyltetraisopalmitate, Mg-ascorbyl phosphate, Na-ascorbyl phosphate,ascorbyl acetate), tocopherol and derivates (such as vitamin-E-acetate,nat. vitamin E and mixtures thereof), vitamin A and derivatives (vitaminA palmitate and acetate) as well as coniferylbenzoat, rutinic acid andderivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol,butyl hydroxytoluene, butyl hydroxyanisole, trihydroxybutyrophenone,urea and its derivatives, mannose and derivatives, zinc and derivatives(e.g. ZnO, ZnSO₄), selenium and derivatives, (e.g. selenomethionine)stilbenes and derivatives (such as stilbenoxide, transstilbenoxide) andsuitable derivatives (salts, esters, ethers, sugars, nucleotides,nucleosides, peptides and lipids) of the named active ingredients. Oneor more preservatives/antioxidants maybe present in an amount of about0.01 wt. % to about 10 wt. % of the total weight of the composition ofthe present invention. Preferably, one or morepreservatives/antioxidants are present in an amount of about 0.1 wt. %to about 1 wt. %.

Examples of emulsifiers that maybe used in the present invention inorder to form O/W, W/O, O/W/O or W/O/W emulsions/microemulsions includesorbitan oleate, sorbitan sesquioleate, sorbitan isostearate, sorbitantrioleate, polyglyceryl-3-diisostearate, polyglycerol esters ofoleic/isostearic acid, polyglyceryl-6 hexaricinolate,polyglyceryl-4-oleate, polygylceryl-4 oleate/PEG-8 propylene glycolcocoate, oleamide DEA, TEA myristate, TEA stearate, magnesium stearate,sodium stearate, potassium laurate, potassium ricinoleate, sodiumcocoate, sodium tallowate, potassium castorate, sodium oleate, andmixtures thereof. Further suitable emulsifiers are phosphate esters andthe salts thereof such as cetyl phosphate (Amphisol® A), diethanolaminecetyl phosphate (Amphisol®), potassium cetyl phosphate (Amphisol® K),sodium glyceryl oleate phosphate, hydrogenated vegetable glyceridesphosphate and mixtures thereof. Furthermore, one or more syntheticpolymers may be used as an emulsifier. For example, PVP eicosenecopolymer, acrylates/C₁₀₋₃₀alkyl acrylate crosspolymer,acrylates/steareth-20 methacrylate copolymer, PEG-22/dodecyl glycolcopolymer, PEG-45/dodecyl glycol copolymer, and mixtures thereof. Thepreferred emulsifiers are cetyl phosphate (Amphisol® A), diethanolaminecetyl phosphate (Amphisol®), potassium cetyl phosphate (Amphisol® K),PVP eicosene copolymer, acrylates/-C₁₀₋₃₀alkyl acrylate crosspolymer,PEG-20 sorbitan isostearate, sorbitan isostearate, and mixtures thereof.Emulsifiers are present in a total amount of about 0.01 wt. % to about20 wt. % of the total weight of the composition of the presentinvention. Preferably, about 0.1 wt. % to about 10 wt. % of emulsifierare used.

The lipid phase may advantageously be chosen from mineral oils andmineral waxes; oils such as triglycerides of caprinic acid or caprylicacid, preferably castor oil; oils or waxes and other natural orsynthetic oils, in a preferred embodiment esters of fatty acids withalcohols e.g. isopropanol, propyleneglycol, glycerin or esters of fattyalcohols with lower carboxylic acids or fatty acids; alkylbenzoates;silicone oils such as dimethylpolysiloxane, diethylpolysiloxane,diphenylpolysiloxane, cyclomethicone and mixtures thereof.

Exemplary fatty substances which may be incorporated into the oil phaseof the emulsion, microemulsion, oleo gel, hydrodispersion orlipodispersion of the present invention are advantageously chosen fromesters of saturated and/or unsaturated, linear or branched alkylcarboxylic acids with 3 to 30 carbon atoms, and saturated and/orunsaturated, linear and/or branched alcohols with 3 to 30 carbon atomsas well as esters of aromatic carboxylic acids and of saturated and/orunsaturated, linear or branched alcohols of 3-30 carbon atoms. Suchesters may advantageously be selected from octylpalmitate, octylcocoate,octylisostearate, octyldodeceylmyristate, cetearylisononanoate,isopropylmyristate, isopropylpalmitate, isopropylstearate,isopropyloleate, n-butylstearate, n-hexyllaureate, n-decyloleat,isooctylstearate, isononylstearate, isononylisononanoate, 2-ethylhexylpalmitate, 2-ethylhexyllaurate, 2-hexyldecylstearate,2-octyldodecylpalmitate, stearylheptanoate, oleyloleate, oleylerucate,erucyloleate, erucylerucate, tridecylstearate, tridecyltrimellitate, andsynthetic, half-synthetic or natural mixtures of such esters e.g. jojobaoil.

Other fatty components suitable for use in the formulation of thepresent invention include polar oils such as lecithines and fatty acidtriglycerides, namely triglycerinic esters of saturated and/orunsaturated, straight or branched carbonic acid with 8 to 24 carbonatoms, preferably of 12 to 18 carbon-atoms whereas the fatty acidtriglycerides are preferably chosen from synthetic, half synthetic ornatural oils (e.g. cocoglyceride, olive oil, sun flower oil, soybeanoil, peanut oil, rape seed oil, sweet almond oil, palm oil, coconut oil,castor oil, hydrogenated castor oil, wheat oil, grape seed oil,macadamia nut oil and others); apolar oils such as linear and/orbranched hydrocarbons and waxes e.g. mineral oils, vaseline(petrolatum); paraffins, squalan and squalen, polyolefines, hydrogenatedpolyisobutenes and isohexadecanes, favored polyolefines are polydecenes;dialkyl ethers such as dicaprylylether; linear or cyclic silicone oilssuch as preferably cyclomethicone (octamethylcyclotetrasiloxane),cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane,poly(methylphenylsiloxane) and mixtures thereof.

Still other fatty components which may advantageously be incorporatedinto formulations of the present invention include isoeikosane;neopentylglycol diheptanoate; propyleneglycol dicaprylate/dicaprate;caprylic/capric/diglycerylsuccinate; butyleneglycol caprylate/caprate;C₁₂₋₁₅alkyllactates; di-C₁₂₋₁₅alkyltartrates; triisostearin;dipentaerythrityl hexacaprylate/hexacaprate; propyleneglycolmonoisostearate; tricaprylin; dimethylisosorbid. Especially beneficialis the use of mixtures of C₁₂₋₁₅alkylbenzoates and2-ethylhexylisostearate, mixtures of C₁₂₋₁₅alkylbenzoates andisotridecylisononanoate as well as mixtures of C₁₂₋₁₅alkylbenzoates,2-ethylhexylisostearate and isotridecylisononanoate.

The oily phase of the formulation of the present invention may alsocontain natural vegetable or animal waxes such as bee wax, china wax,bumblebee wax and other waxes of insects as well as shea butter andcocoa butter.

A moisturizing agent may be incorporated into a composition of thepresent invention to maintain hydration or rehydrate the skin.Moisturizers that prevent water from evaporating from the skin byproviding a protective coating are called emollients. Additionally anemollient provides a softening or soothing effect on the skin surfaceand is generally considered safe for topical use. Preferred emollientsinclude mineral oils, lanolin, petrolatum, capric, caprylictriglyceraldehydes, cholesterol, silicones such as dimethicone,cyclomethicone, almond oil, jojoba oil, avocado oil, castor oil, sesameoil, sunflower oil, coconut oil and grape seed oil, cocoa butter, oliveoil aloe extracts, fatty acids such as oleic and stearic, fatty alcoholssuch as cetyl and hexadecylalcohol, diisopropyl adipate, hydroxybenzoateesters, benzoic acid esters of C₉₋₁₅-alcohols, isononyl iso-nonanoate,ethers such as polyoxypropylene butyl ethers and polyoxypropylene cetylethers, and C₁₂₋₁₅alkyl benzoates, and mixtures thereof. The mostpreferred emollients are hydroxybenzoate esters, aloe vera, C₁₂₋₁₅alkylbenzoates, and mixtures thereof. An emollient may be present in anamount of about 1 wt. % to about 20 wt. % of the total weight of thecomposition. The preferred amount of emollient may be about 2 wt. % toabout 15 wt. %, and most preferably about 4 wt. % to about 10 wt. %.

Moisturizers that bind water, thereby retaining it on the skin surfaceare called humectants. Suitable humectants may be incorporated into acomposition of the present invention such as glycerin, polypropyleneglycol, polyethylene glycol, lactic acid, pyrrolidon carboxylic acid,urea, phopholipids, collagen, elastin, ceramides, lecithin sorbitol,PEG-4, and mixtures thereof. Additional suitable moisturizers arepolymeric moisturizers of the family of water soluble and/or swellable/and/or with water gelating polysaccarides such as hyaluronic acid,chitosan and/or a fucose rich polysaccharide which is e.g. available asFucogel® 1000 (CAS-Nr. 178463-23-5) by SOLABIA S. One or more humectantsare optionally present at about 0.5 wt. % to about 8 wt. % in acomposition of the present invention, preferably about 1 wt. % to about5 wt. %.

The aqueous phase of the compositions of the present invention maycontain usual cosmetic additives such as alcohols, especially loweralcohols, preferably ethanol and/or isopropanol, low diols oder polyolsand their ethers, preferably propylenglycols, glycerin, ethyleneglycol,ethyleneglycol monoethyl- or monobutyl-ether, propyleneglycol-mono-methyl-, monoethyl- or monobutyl ether, diethyleneglycol-monomethyl- or monoethylether and analogue products, polymers,foam stabilisators; electrolytes and especially one or more thickeners.Thickeners that may be used in formulations of the present invention toassist in making the consistency of a product suitable include carbomer,siliciumdioxide, magnesium and/or aluminum silicates, beewax, stearicacid, stearyl alcohol polysaccharides and their derivatives such asxanthan gum, hydroxypropyl cellulose, polyacrylamides, acrylatecrosspolymers preferably a carbopole, such as carbopole of type 980,981, 1382, 2984, 5984 alone or mixtures thereof. Suitable neutralizingagents which may be included in the composition of the present inventionto neutralize components such as e.g. an emulsifier or a foambuilder/stabilizer include but are not limited to alkali hydroxides suchas a sodium and potassium hydroxide; organic bases such asdiethanolamine (DEA), triethanolamine (TEA), aminomethyl propanol, andmixtures thereof; amino acids such as arginine and lysine and anycombination of any foregoing. The neutralizing agent may be present inan amount of about 0.01 wt. % to about 8 wt. % in the composition of thepresent invention, preferably, 1 wt. % to about 5 wt. %.

The addition of electrolytes into the composition of the presentinvention may be necessary to change the behavior of a hydrophobicemulsifier. Thus the emulsions/microemulsions of this invention maypreferably contain electrolytes of one or several salts including anionssuch as a chloride, a sulfate, a carbonate, a borate or an aluminate,without being limited thereto. Other suitable electrolytes may be on thebases of organic anions such as, but not limited to, lactate, acetate,benzoate, propionate, tartrate and citrate. As cations preferablyammonia, alkylammonia, alkali or alkaline earth metals, magnesium, ironor zinc ions are selected. Especially preferred salts are potassium andsodium chloride, magnesium sulfate, zinc sulfate and mixtures thereof.Electrolytes are present in an amount of about 0.01 wt. % to about 8 wt.% in the composition of the present invention.

The cosmetic compositions of the invention are useful as compositionsfor photoprotecting the human epidermis or hair against the damagingeffect of ultraviolet irradiation, as antisun/sunscreen composition oras makeup product. Such compositions can, in particular, be provided inthe form of a lotion, a thickened lotion, a gel, a cream, a milk, anointment, a powder or a solid tube stick and may optionally be packagedas an aerosol and may be provided in the form of a mousse, foam or aspray. When the cosmetic composition according to the invention isprovided for protecting the human epidermis against UV radiation or asantisun/sunscreen composition, it may be in the form of a suspension ordispersion in solvents or fatty substances, or alternatively in the formof an emulsion or microemulsion (in particular of O/W or W/O type, O/W/Oor W/O/W-type), such as a cream or a milk, a vesicular dispersion, inthe form of an ointment, a gel, a solid tube stick or an aerosol mousse.The emulsions can also contain anionic, nonionic, cationic or amphotericsurfactants.

When the cosmetic composition according to the invention is used forprotecting the hair, it may be in the form of a shampoo, a lotion, a gelor a rinse out composition, to be applied before or after shampooing,before or after dyeing or bleaching, before, during or afterpermanent-waving or hair straightening operation, a styling or treatmentlotion or a gel, a blow-drying or hairsetting lotion or gel, a hairlacquer, or a composition for permanent-waving, straightening, dyeing orbleaching the hair.

When the cosmetic composition according to the invention is used asmakeup product for eyelashes, the eyebrows, the skin or the hair, suchas an epidermal treatment cream, a foundation, a tube of lipstick, aneyeshadow, a face powder, an eyeliner, a mascara or a coloring gel, itmay be solid or pasty, anhydrous or in aqueous form, such as O/W or W/Oemulsion, suspension or gel.

The present invention also features formulating the compounds of formulaI and II as an agent for screening out UV radiation, in particular forcontrolling the color of human skin.

This invention also features non-therapeutic regime/regimen forprotecting the skin and/or hair against ultraviolet radiation, inparticular solar radiation, comprising topically applying an effectiveamount of a cosmetic composition as described above, or of a compound offormula I or II.

Finally, this invention also features non-therapeutic regime/regimen forcontrolling the variation of the color of the skin caused by ultravioletradiation, comprising topically applying onto the skin an effectiveamount of a cosmetic composition as described above, or of a compound offormula I or II.

The following examples are provided to further illustrate the processesand compositions of the present invention. These examples areillustrative only and are not intended to limit the scope of theinvention in any way. In the Examples, FC. means Flash chromatography;HV means high vacuum (0.1 Pa or below).

EXAMPLE 1 Preparation of Ethyl (2,6-dimethyl-pyran-4-ylidene)Cyanoacetate

To a mixture of 9.45 ml (100 mmol) acetic anhydride and 1.06 ml (10mmol) ethylcyano acetate 1.24 g (10 mmol) of 1,4-dimethyl-γ-pyrones wasadded. The reaction mixture was refluxed for 20 h at 155° C. Afterevaporation of the acetic anhydride the residue was extracted with ether(2×50 ml). The combined organic phases were subsequently washed withwater (3×30 ml) and saturated NaCl-solution (1×30 ml). After drying(Na₂SO₄), the solvent was evaporated (HV) and the crude product purifiedvia FC (n-hexane/EtOAC 7:3) yielding 0.15 g (7%) of ethyl(2,6-dimethyl-pyran-4-ylidene) cyanoacetate as a solid.

¹H-NMR (300 MHZ, CDCl₃): 7.90 (s, 1H), 6.60 (s, 1H), 4.2 (q, 2H, —OCH₂),2.29 (s, 6H, CH₃), 1.32 (t, 3H, CH₃). MS (EI): 219 (100, M⁺), 191 (13),174 (83), 147 (64), 122 (9), 91 (4), 43 (11), 29 (3). IR (neat): 2987w,2193s, 1697s, 1649vs, 1582s, 1513s, 1459m, 1407m, 1390w, 1362m, 1338s,1251vs (br.), 1212s, 1173s, 1135s, 1059m,1025m cm⁻¹. M.p.: 163-164° C.,UV: λ_(max)=348 nm (ε=24′982).

EXAMPLE 2 Preparation of 2-ethylhexyl (2,6-dimethyl-pyran-4-ylidene)Cyanoacetate

To a suspension of 1.72 g (10 mmol) of(2,6-dimethyl-4H-pyran-4-ylidene)malononitril in 33 ml of2-ethyl-1-hexanol, 3.3 ml of water and 3.3 ml of concentrated H₂SO₄ wereadded. The reaction mixture was refluxed at 100° C. for 48 h. Afteraddition of 50 ml of water the resulting solution was extracted withwith ether (2×100 ml). The organic phase was washed with water (2×50 ml)and with saturated NaCl-solution (1×50 ml). After drying (Na₂SO₄), thesolvent was evaporated (HV) and the crude product was purified via FC(n-hexane/EtOAC 85:15) yielding 1.71 g (56%) of 2-ethylhexyl(2,6-dimethyl-pyran-4-ylidene) cyanoacetate as a slightly yellow solid.

¹H-NMR (300 MHZ, CDCl₃): 7.90 (s, 1H), 6.60 (s, 1H), 4.08 (m, 2H,—OCH₂), 2.29 (s, 6H, CH₃), 1.65 (m, 1H), 1.50-1.20 (m, 8H), 0.90 (m, 6H,2CH₃). MS (EI): 303 (28, M⁺), 191 (100), 174 (41), 147 (27). IR (neat):2958m, 2931m, 2873w, 2198m, 1696s, 1656vs, 1585m, 1523s, 1459m, 1410m,1379w, 1341s, 1274m, 1252s (br.), 1213m, 1176m, 1131m, 1062m, 1038wcm⁻¹. M.p.: 64-65° C., UV: λ_(max)=352 nm (ε=25′548).

EXAMPLE 3 Preparation of2-(2,6-diethyl-3,5-dimethylpyran-4-ylidene)malononitrile

To a solution of 0.33 g (5 mmol) of malonodinitrile in 2.4 ml (25 mmol)acetic anhydride 1.20 g (5 mmol) of 2,6-diethyl-3,5-dipropyl-pyran-4-one(prepared according to J. Chem. Soc (C), 1967, 828-830) was added. Afteraddition of 150 ml of water the resulting solution was extracted twicewith ether (50 ml). The combined organic phases were washed with water(2×50 ml) and with saturated NaCl-solution (1×30 ml). After drying(Na₂SO₄), the solvent was evaporated (HV) and the crude product waspurified via FC (n-hexane/EtOAC 7:3) yielding 0.54 g (47%) of2-(2,6-diethyl-3,5-dimethylpyran-4-ylidene)malononitrile as a brownsolid.

¹H-NMR (300 MHZ, CDCl₃): 2.64 (q, 4H, 2CH₂), 2.35 (s, 6H, 2CH₃) 1.21 (s,6H, 2CH₃). MS (EI): 228 (100, M⁺), 213 (3), 201(5),200 (5),188 (48), 163(9), 57 (8), 43 (3), 29 (4). IR (neat): 2986m, 2942m, 2343w (br.),2193s, 1622vs, 1551s, 1428s (br.), 1387s, 1203m, 1189s, 1169s, 1082m,1033s cm⁻¹. M.p.: 64-65° C., UV: λ_(max)=366 nm (ε=22′808).

EXAMPLE 4 Preparation of2-(3,5-diethyl-2,6-dipropylpyran-4-ylidene)malononitrile

2-(3,5-Diethyl-2,6-dipropylpyran-4-ylidene)malononitrile was prepared inanalogy to the procedure of example 3.

¹H-NMR (300 MHZ, CDCl₃): 2.90 (q, 4H, 2CH₂) 2.60 (t, 4H, 2CH₂), 1.70 (m,2H, 2CH₂), 1.22 (t, 6H, 2CH₃) 1.00 (t, 6H, 2CH₃). MS (EI): 284 (54, M⁺),269 (100), 256 (10), 244 (18), 230 (9), 216 (9), 203 (7), 71 (3), 43(10). IR (neat): 2965m, 2934w, 2875w, 2198s, 1615vs, 1550w, 1443s (br.),1379m, 1325w, 1255w, 1178m, 1155m, 1055m, 956m cm⁻¹, UV: λ_(max)=364 nm(ε=21′729).

EXAMPLE 5 Preparation of1-N-(2-ethylhexyl)-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine

A solution of 0.5 g (2.9 mmol) of(2,6-dimethyl-4H-pyran-4-ylidene)malononitril in 7.6 ml (6 g, 46.4 mmol)2-ethyl-1-hexylamine was refluxed for 1 h under nitrogen. Removal of theexcess of ethyl-1-hexylamine at reduced pressure left a solid which wasrecrystallized from 15 ml EtOAc/MeOH 2/1 yielding 0.45 g (55%) of1-N-(2-ethylhexyl)-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine.

¹H-NMR (300 MHZ, CDCl₃): 6.7 (s, 2H, H—C(3), H—C(5)), 3.85 (d, 2H,H—C(1′)), 2.42 (s, 6H, —CH₃), 1.7 (m, 1H, H—C(2′)), 1.41-1.12 (m, 8H,CH₂), 0.9 (2t, 6H, 2CH₃). MS (CI): 284.3 (M+H⁺). IR (neat): 2966m,2932m, 2860w, 2187s, 2164vs, 1638vs, 1552s, 1499s, 1469m, 1372s, 1347s,1221m, 1185s, 1067m, 1036w cm⁻¹. M.p.: 187° C., UV: λ_(max)=372 nm(ε=39′687).

EXAMPLE 6 Preparation of Compounds in Analogy to Example 1

In analogy to the procedure of Example 1, the following compounds wereobtained:

1-N-dodecyl-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine.

¹H-NMR (300 MHZ, CDCl₃): 6.69 (s, 2H, H—C(3), H—C(5)), 3.88 (m, 2H,H—C(1′)), 2.45 (s, 6H, —CH₃), 1.68 (m, 2H, H—C(2′)), 1.45-1.20 (m, 19H,CH₂), 0.88 (t, 3H,—CH₃). MS (EI): 339 (M⁺,100), 324 (73), 310 (13),296(10), 282(12), 268 (10), 254 (13), 240 (8), 226 (6), 212 (7), 198(8), 185 (14), 171 (27), 57 (10), 43 (15). IR (neat): 2914vs, 2815vs,2189vs, 2163vs, 1644vs, 1554s, 1504m, 1472s, 1359s, 1314m, 1223m, 1188s,1127w, 1069m, 1037w cm⁻¹. M.p.: 161-162° C. UV: λ_(max)=370 nm(ε=42′538).

1-N-[3-(2-ethylhexyloxy)propyl]-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine.

¹H-NMR (300 MHZ, CDCl₃): 6.69 (s, 2H, H—C(3), H—C(5)), 4.05 (m, 2H,H—C(1′)), 3.46 (t, 2H, H—C(3′), 3.31 (d, 2H, H—C(1″), 2.48 (s, 6H,—CH₃), 1.93 (m, 2H, H—C(2′)), 1.50 (m, 2H, H—C(2″)), 1.40-1.20 (m, 8H,CH₂), 0.90 (2t, 6H, 2CH₃). MS (CI): 342 (M+H⁺). IR (neat): 2957m, 2928m,2858m, 2189vs, 2163vs, 1644vs, 1553s, 1503m, 1482m, 1461m, 1379m,1356vs, 1312w, 1223w, 1191s, 1107s (br.), 1068m, 1037m cm⁻¹. M.p.:116-117° C. UV: λ_(max)=370 nm (ε=37′846).

1-N-[3,5,5-trimethylhexyl]-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine.

¹H-NMR (300 MHZ, CDCl₃): 6.62 (s, 2H, H—C(3), H—C(5)), 3.9 (m, 2H,H—C(1′)), 2.49 (s, 6H, —CH₃), 1.70 (m, 2H, H—C(2′)), 1.55 (m, 2H,H—C(3′)), 1.20 (m, 2H, H—C(4′)), 1.05 (d, 2H, CH₃), 0.92 (s, 9H, 3CH₃).MS (CI): 298 (M+H⁺). IR (neat): 2954m, 2192vs, 2171vs, 1626vs, 1554m,1503m, 1481m, 1422w, 1388m, 1344vs, ,1224w, 1189s, 1107s, 1069m, 1036mcm⁻¹. M.p.: 236-237-117° C. UV: λ_(max)=372 nm (ε=39′569).

1-N-methyl-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine.

¹H-NMR (300 MHZ, CDCl₃): 6.65 (s, 2H, H—C(3), H—C(5)), 3.61 (s, 3H,—NCH₃), 2.49 (s, 6H, —CH₃). MS (EI): 185 (M⁺). IR (neat): 2962w, 2185vs,2161vs, 1635vs, 1555s, 1495s, 1422m, 1383m, 1354vs, 1223w, 1195s, 1067s,1038m cm⁻¹. M.p.: >250° C. UV:λ_(max)=368 nm (ε=36′280).

1-N-butyl-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine.

¹H-NMR (300 MHZ, CDCl₃): 6.65 (s, 2H, H—C(3), H—C(5)), 3.90 (m, 2H,H—C(1′)), 2.49 (s, 6H, —CH₃), 1.69 (m, 2H, H—C(2′)), 1.45 (m, 2H,H—C(3′)), 1.005 (s, 3H, —CH₃). MS (CI): 228 (M+H⁺). IR (neat): 2956w,2869w, 2191vs, 2167vs, 1633vs, 1553s, 1499s, 1479m, 1383m, 1361vs,1338s, 1223m, 1185s, 1112m, 1067s cm⁻¹. M.p.: 198° C. UV: λ_(max)=370 nm(ε=37′300).

EXAMPLE 7 Preparation of 2-ethylhexyl(1-N-butyl-2,6-dimethyl-1H-pyridin-4-ylidene)cyanoacetate

A solution of 0.30 g (1 mmol) of 2-ethylhexyl(2,6-dimethyl-pyran-4-ylidene)cyanoacetate (prepared as described inexample 1) in 4 ml butylamine was refluxed at 80° C. for 1 h undernitrogen. Removal of the excess of butylamine at reduced pressure left aorange oil which was purified by FC (n-hexane/EtOAc 1:1) yielding 0.23 g(64%) of 2-ethylhexyl(1-N-butyl-2,6-dimethyl-1H-pyridin-4-ylidene)cyanoacetate as a slightlyyellow solid.

¹H-NMR (300 MHZ, CDCl₃): 8.20 (s, 1H), 6.86 (s, 1H), 4.05 (m, 2H,—OCH₂), 3.85 (t, 2H, —NCH₂) 2.45 (s, 6H, CH₃), 1.65 (m, 3H),1.50-1.20(m, 10H), 1.01 (t, 3H, CH₃), 0.9 (m, 6H, 2CH₃). MS (CI): 359(M+H⁺). IR (neat): 2960m, 2929m, 2858w, 2177vs, 1665vs, 1619vs, 1546m,1501s, 1479s, 1380s, 1354s, 1316m, 1252s, 1190m, 1114m, 1056s (br.)cm⁻¹. M.p.: 69-70° C., UV: λ_(max)=374 nm (ε=39′654)

EXAMPLE 8 Preparation of 2-ethylhexyl(1-N-[3-(2-ethylhexyloxy)propyl]-2,6-di-methyl-1H-pyridin-4ylidene)cyanoacetate

In analogy to Example 11 there was obtained 2-ethylhexyl(1-N-[3-(2-ethylhexyloxy)-propyl]-2,6-dimethyl-1H-pyridin-4-ylidene)cyanoacetate.

¹H-NMR (300 MHZ, CDCl₃): 8.20 (s, 1H), 6.85 (s, 1H), 4.05 (m, 2H, —NCH₂,—OCH₂), 3.46 (t,2H, —OCH₂), 3.31 (d, 2H, CH₂), 2.45 (s, 6H, CH₃), 1.90(m, 2H), 1.65 (m, 1H), 152-1.20 (m, 17H), 0.89 (m, 12H, 4CH₃), 0.9 (m,6H, 2CH₃). MS (CI): 473 (M+H⁺). IR (neat): 2958m, 2926m, 2858m, 2179m,1671s, 1620vs, 1547ImI, 1503m, 1483s, 1375m, 1349s, 1307m, 1253vs,1188m, 1103s, 1053vs, cm⁻¹. M.p.: 69-70° C., UV: λ_(max)=366 nm(ε=46′163).

EXAMPLE 9 Preparation of2-{1-[3-(2-{2-[3-(4-dicyanomethylene-2,6-dimethyl-4H-pyridin-1-yl)-propoxy]-ethoxy}-ethoxy)-propyl]-2,6-dimethyl-1H-pyridin-4-ylidene}-malononitrile

A solution of 0.52 g (3 mmol) of(2,6-dimethyl-4H-pyran-4-ylidene)malononitril and 0.3 ml (1.5 mmol) of4,7,10-trioxa-1,13-tridecanediamine in 6 ml of acetontrile was heated to90° C. for 70 h under nitrogen. Removal of the acetonitrile left a brownresidue which was recrystallized from 25 ml methanol and 10 ml ethylacetate yielding 0.68 g (43%) of2-{1-[3-(2-{2-[3-(4-dicyanomethylene-2,6-dimethyl-4H-pyridin-1-yl)-propoxy]-ethoxy}-ethoxy)-propyl]-2,6-dimethyl-1H-pyridin-4-ylidene}-malononitrile.

¹H-NMR (300 MHZ, CDCl₃): 6.62 (s, 4H, H—C(3), H—C(5)), 4.10 (m, 4H,H—C(1′)), 3.62 (s, 8H, —OCH₂CH₂O—), 3.55 (t, 4H, H—C(3′)), 2.50 (s, 6H,—CH₃), 2.00 (m, 4H, H—C(2′)). MS (CI): 529 (M+H⁺). IR (neat):3521w(br.), 2868w, 2191s, 2163s, 1648vs, 1553s, 1504m, 1484w, 1380w,1357s, 1313w, 1223w, 1192m, 1102m (br.), 1070m, 1037m cm⁻¹. M.p.:138-139° C., UV: λ_(max)=372 nm (ε=67′608).

EXAMPLE 10 Preparation of an Oil-in-water Sun Milk

An oil-in-water sun milk can be prepared with the following ingredientsIngredients INCI Nomenclature % w/w A Compound of 0.1-25 formula I or IILanette O Cetearyl Alcohol 2.00 Myritol 318 Caprylic/capric Triglyceride6.00 Mineral oil Mineral oil 2.00 Vitamin E acetate Tocopheryl Acetate1.00 Prisorine 3515 Isostearyl Alcohol 4.00 Edeta BD Disodium EDTA 0.10Phenonip Phenoxyethanol & Methylparaben & 0.60 Ethylparaben &Propylparaben & Butylparaben AMPHISOL K Potassium Cetyl Phosphate 2.00 BWater deionized Aqua ad 100 1,2-Propylen Glycol Propylene Glycol 5.00Carbopol 981 Carbomer 0.30 C KOH 10% solution Potassium Hydroxyde 2.10Procedure: Heat part A) and B) to 85° C. while stirring. Whenhomogeneous, add part B) to A) under agitation. Cool to about 45° C.while stirring. Then add part C). Homogenize at 11000 rpm to achieve asmall particle size. Cool to ambient temperature while stirring.

EXAMPLE 11 Preparation of an Oil-in-water Sun Milk with Pigments

An oil-in-water sun milk with pigments is prepared with the followingingredients Ingredients INCI Nomenclature % w/w A PARSOL SLX DimethicoDiethylbenzalmalonate 6.00 Compound of 0.1-25 formula I or II NeoHeliopan AP 2,2-(1,4-phenylene)bis-(1H- 3.00 benzimidazol-4,6-disulfonicacid) Tinosorb S 2,4-Bis((4-(ethyl-hexylox)-2- 3.00hydroxy)-phenyl)-6-(4- methoxyphenyl)-1,3,5-triazine Lanette O CetearylAlcohol 2.00 Myritol 318 Caprylic/capric Triglyceride 6.00 Mineral oilMineral oil 2.00 Vitamin E acetate Tocopheryl Acetate 1.00 Prisorine3515 Isostearyl Alcohol 4.00 Edeta BD Disodium EDTA 0.10 PhenonipPhenoxyethanol & Methylparaben 0.60 & Ethyl-paraben & Propylparaben &Butylparaben AMPHISOL K Potassium Cetyl Phosphate 2.00 B Water deionizedAqua ad 100 1,2-Propylen Glycol Propylene Glycol 5.00 Carbopol 981Carbomer 0.30 Tinosorb M Methylene Bis-Benzotriazolyl 6.00Tetramethyl-butylphenol C KOH 10% solution Potassium Hydroxyde 2.10Heat part A) and B) to 85° C. while stirring. When homogeneous, add partB) to A) under agitation. Cool to about 45° C. while stirring Then addpart C). Homogenize at 11000 rpm to achieve a small particle size. Coolto ambient temperature while stirring.

EXAMPLE 12 Preparation of a Water-resistant Sun Milk

A water-resistant sun milk is prepared with the following ingredientsIngredients INCI Nomenclature % w/w A PARSOL SLX DimethicoDiethylbenzalmalonate 6.00 PARSOL 1789 Butyl Methoxydibenzoylmethane2.00 Compound of 0.1-25% formula I or II Parsol 5000 4-MethylbenzylideneCamphor 4.00 Parsol MCX Ethylhexylmethoxycinnamate 6.00 Uvinul T 150Ethylhexyltriazone 2.00 Silicone DC Dimethicone 1.00 200/350 cs LanetteO Cetearyl Alcohol 2.00 Softisan 100 Hydrogenated Coco-Glycerides 3.00Tegosoft TN C12-15 Alkyl Benzoate 6.00 Cetiol B Dibutyl Adipate 7.00Vitamin E acetate Tocopheryl Acetate 2.00 Berkemyol Palmitoyl Grape seedExtract 1.00 (Grape Seed) BHT BHT 0.05 Edeta BD Disodium EDTA 0.10Phenonip Phenoxyethanol & Methylparaben & 0.60 Ethylparaben &Propylparaben & Butylparaben AMPHISOL Cetyl Phosphate DEA 2.00 B Waterdeionized Aqua ad 100 Propylene Glycol Propylene Glycol 5.00 Carbopol980 Carbomer 0.30 C KOH (10% sol.) Potassium Hydroxide 1.50Heat part A) and B) to 85° C. while stirring. When homogeneous, add partB) to A) under agitation. Cool to about 45° C. while stirring Then addpart C). Homogenize at 11000 rpm to achieve a small particle size. Coolto ambient temperature while stirring.

EXAMPLE 13 Preparation of a Sun Milk for Babies and Children

A sun milk for babies and children is prepared with the followingingredients Ingredients INCI Nomenclature % w/w A Compound of 0.1-25formula I or II Titanium Dioxide Titanium Dioxide microfine 4.00Tegosoft TN C12-15 Alkyl Benzoate 5.00 Silicone 2503 Stearyl Dimethicone2.00 Cosmetic Wax Cetyl Alcohol Cetyl Alcohol 1.00 Butylated BHT 0.05Hydroxytoluene Estol GMM 3650 Glyceryl Myristate 4.00 Edeta BD DisodiumEDTA 0.10 Phenonip Phenoxyethanol & Methylparaben & 0.60 Ethylparaben &Propylparaben & Butylparaben AMPHISOL A Cetyl Phosphate 2.00 B Waterdeionized Aqua ad 100 Carbopol 980 Carbomer 10.00 Glycerine Glycerine3.00 C KOH sol. 10% Potassium Hydroxide 0.50Heat part A) and B) to 85° C. while stirring. When homogeneous, add partB) to A) under agitation. Cool to about 45° C. while stirring Then addpart C). Homogenize at 11000 rpm to achieve a small particle size. Coolto ambient temperature while stirring.

EXAMPLE 14 Preparation of a High Protective Sun Milk

A high protective sun milk is prepared with the following ingredientsIngredients INCI Nomenclature % w/w A PARSOL SLX DimethicoDiethylbenzalmalonate 6.00 PARSOL 1789 Butyl Methoxydibenzoylmethane2.00 Compound of 0.1-25% formula I or II Parsol 5000 4-MethylbenzylideneCamphor 4.00 Parsol MCX Ethylhexylmethoxicinnamate 6.00 Uvinul T 150Ethylhexyl Triazone 2.00 Silicone DC Dimethicone 1.00 200/350 cs LanetteO Cetearyl Alcohol 2.00 Softisan 100 Hydrogenated Coco-Glycerides 3.00Tegosoft TN C12-15 Alkyl Benzoate 6.00 Cetiol B Dibutyl Adipate 7.00Vitamin E acetate Tocopheryl Acetate 2.00 Berkemyol Palmitoyl Grape seedExtract 1.00 (Grape Seed) BHT BHT 0.05 Edeta BD Disodium EDTA 0.10Phenonip Phenoxyethanol & Methylparaben & 0.60 Ethylparaben &Propylparaben & Butylparaben AMPHISOL K Potassium Cetyl Phosphate 2.00 BWater deionized Aqua ad 100 Propylene Glycol Propylene Glycol 5.00Carbopol 980 Carbomer 0.30 C KOH (10% sol.) Potassium Hydroxide 1.50Heat part A) and B) to 85° C. while stirring. When homogeneous, add partB) to A) under agitation. Cool to about 45° C. while stirring Then addpart C). Homogenize at 11000 rpm to achieve a small particle size. Coolto ambient temperature while stirring.

EXAMPLE 15 Preparation of a Water-free Sun Gel

A water-free sun gel is prepared with the following ingredientsIngredients INCI Nomenclature % w/w A PARSOL MCX EthylhexylMethoxycinnamate 6.00 PARSOL 1789 Butyl Methoxydibenzoylmethane 4.00PARSOL 5000 4-Methylbenzylidene Camphor 4.00 Compound of 0.1-25% formulaI or II Uvasorb HEB Diethylhexyl Butamido Triazone 1.50 Vitamin Eacetate Tocopheryl Acetate 1.50 Tegosoft TN C12-15 Alkyl Benzoate 9.00Elefac I-205 Ethylhexyldodecyl Neopentanoate 2.00 Alcohol Alcohol ad100.00 Isopropyl Alcohol Isopropyl Alcohol 20.00 B Klucel MFHydroxypropylcellulose 2.00Heat part A) to 85° C. while stirring. When homogeneous, add part B) toA) under agitation. Cool to ambient temperature while stirring.

EXAMPLE 16 Preparation of a Sun Gel

A sun gel is prepared with the following ingredients Ingredients INCINomenclature % w/w A Pemulen TR-2 Acrylates/C10-30 Alky 0.60 AcrylateCrosspolymer Phenonip Phenoxyethanol & Methylparaben & 0.60 Ethylparaben& Propylparaben & Butylparaben Edeta BD Disodium EDTA 0.1 Aqua Aqua ad100 Compound of 0.01-25 formula I or II B PARSOL MCX EthylhexylMethoxycinnamate 5.00 PARSOL 1789 Butyl Methoxydibenzoylmethane 4.00PARSOL 340 Octocrylene 3.00 Tegosoft TN C12-15 Alkyl Benzoate 15.00Antaron V-216 PVP/Hexadecene Copolymer 1.00 Vitamin E acetate TocopherylAcetate 0.50 Uvinul TiO2 Titanium Dioxide and 5.00Trimethoxycaprylylsilane Butylated BHT 0.05 Hydroxytoluene Cremophor RH410 PEG-40 Hydrogenated Castor Oil 0.50 C Tris Amino Tromethamine 0.50 DParfum Parfum q.s.Heat part A) and B) to 85° C. while stirring. When homogeneous, add partB) to A) under agitation. Cool to about 45° C. while stirring.Homogenize at 11000 rpm to achieve a small particle size. Cool toambient temperature while stirring. Then add part C) and D).

EXAMPLE 17 Preparation of a High Protection Water-in-oil Sun Milk

A high protection water-in-oil sun milk is prepared with the followingingredients Ingredients INCI Nomenclature % w/w A PARSOL MCX EthylhexylMethoxycinnamate 6.00 PARSOL 1789 Butyl Methoxydibenzoylmethane 2.00PARSOL 5000 4-Methylbenzylidene Camphor 4.00 Uvinul T 150 EthylhexylTriazone 2.00 Uvinul TiO2 Titanium Dioxide and 5.00Trimethoxycaprylylsilane Compound of 0.1-25 formula I or II Arlacel P135 PEG-30 Dipolyhydroxystearate 2.00 Tegosoft TN C12-15 Alkyl Benzoate5.00 Cosmacol EMI Di-C12-13 Alkyl Malate 6.00 Miglyol 840 PropyleneGlycol Dicaprylate/Dicaprate 6.00 Butylated BHT 0.05 HydroxytoluenePhenonip Phenoxyethanol & Methylparaben & 0.60 Ethylparaben &Propylparaben & Butylparaben B Deionized water Aqua ad 100 GlycerinGlycerin 5.00 Edeta Disodium EDTA 0.1 NaCl Sodium Chloride 0.30 C ParsolHS Phenylbenzyimidazole Sulphonic Acid 4.00 Water Aqua 20.00Triethanolamine Triethanolamine 2.50 99%.Heat part A) and B) to 85° C. while stirring. When homogeneous, add partB) to A) under agitation. Cool to about 45° C. while stirring Then addpart C). Homogenize at 11000 rpm to achieve a small particle size. Coolto ambient temperature while stirring.

EXAMPLE 18 Preparation of a Water-in-oil Milk with Pigments

A water-in-oil milk with pigments can be prepared with the followingingredients Ingredients INCI Nomenclature % w/w A Cremophor WO 7 PEG-7Hydrogenated Castor Oil 6.00 Elfacos ST 9 PEG-45/Dodecyl GlycolCopolymer 2.00 Parsol MCX Ethylhexyl Methoxycinnamate 5.00 Parsol 1789Butyl Methoxydibenzoylmethane 3.00 Compound of 0.1-25 formula I or IITinosorb S 2,4-Bis((4-(ethyl-hexylox)-2-hydroxy)- 3.00phenyl)-6-(4-methoxyphenyl)-1,3,5- triazine Parsol 50004-Methylbenzylidene Camphor 4.00 Uvinul TiO2 Titanium Dioxide and 2.00Trimethoxycaprylylsilane Microcrystalline Microcrystalline Wax 2.00 waxMiglyol 812 Caprylic/capric Triglyceride 5.00 Vitamin E acetateTocopheryl Acetate 1.00 Jojoba oil Simmondsia Chinensis Seed Oil 5.00Edeta BD Disodium EDTA 0.10 Butylated BHT 0.05 Hydroxytoluene PhenonipPhenoxyethanol & Methylparaben & 0.60 Ethylparaben & Propylparaben &Butylparaben B Water deionized Aqua ad 100 Glycerin Glycerin 5.00 C NeoHeliopan AP 2.00 Water deionized Aqua 20.00 KOH 10% Potassium Hydroxide4.00 solutionProcedure: Heat part A) and B) to 85° C. while stirring. Whenhomogeneous, add part B) to A) under agitation. Cool to about 45° C.while stirring. Then add part C). Homogenize at 11000 rpm to achieve asmall particle size. Cool to ambient temperature while stirring.

EXAMPLE 19 Preparation of a Hair Conditioner

A hair conditioner can be prepared with the following ingredientsIngredients INCI Nomenclature % w/w A Lanette O Cetearyl Alcohol 3.00Cetiol LC Coco Caprylate/Caprate 2.50 Phenonip Phenoxyethanol &Methylparaben & 0.60 Ethylparaben & Propylparaben & ButylparabenCremophor A6 Ceteareth-6 & Stearyl Alcohol 2.00 Cremophor A25Ceteareth-25 2.00 Compound of 0.1-25 formula I or II B Parsol SLXDimethico-diethylbenzalmalonate 1.00 Tween 80 Polysorbate 80 q.s. CWater Aqua ad. 100 EDETA BD Disodium EDTA 0.20 Carbopol 980 Carbomer0.20 D Panthenol 75% Panthenol 0.50 E Triethanolamine Triethanolamineq.s. 100Procedure: Heat part A) and B) to 85° C. while stirring. Whenhomogeneous, add part B) to A) under agitation. Cool to about 45° C.while stirring. Add part C). Homogenize at 11000 rpm to achieve a smallparticle size. Cool to ambient temperature while stirring. Then addparts D) and E).

EXAMPLE 20 Preparation of a Protective Day Cream with Vitamin C

A protective Day cream with Vitamin C can be prepared with the followingingredients Ingredients INCI Nomenclature % w/w A PARSOL SLX DimethicoDiethylbenzalmalonate 4.00 PARSOL 1789 Butyl Methoxydibenzoylmethane1.50 Glyceryl Myristate Glyceryl Myristate 2.00 Compound of formula0.1-25 I or II Cetyl Alcohol Cetyl Alcohol 0.50 Myritol 318Caprylic/Capric Triglyceride 5.00 Crodamol DA Diisopropyl Adipate 5.00Vitamin E acetate Tocopheryl Acetate 2.00 Butylated BHT 0.05Hydroxytoluene Phenonip Phenoxyethanol & 0.60 Methylparaben &Ethylparaben & Propylparaben & Butylparaben Edeta BD Disodium EDTA 0.10AMPHISOL K Potassium Cetyl Phosphate 2.00 B Water deionized Aqua ad 1001,2-Propylene Glycol Propylene Glycol 2.00 D-PANTHENOL 75 L Panthenol2.00 Ethanol Ethanol 5.00 Allantoin Allantoin 0.20 Carbopol ETD 2001Carbomer 0.30 C KOH 10% sol. Potassium Hydroxide 1.50 D Water Aqua 10.00STAY-C 50 Sodium Ascorbyl Phosphate 0.50 E Perfume Perfume q.s.Procedure: Heat part A) and B) to 85° C. while stirring. Whenhomogeneous, add part B) to A) under agitation. Cool to about 45° C.while stirring. Add part C) . . . Homogenize at 11000 rpm to achieve asmall particle size. Cool to ambient temperature while stirring. Thenadd parts D) and E).

EXAMPLE 21 Preparation of a Pearly Shampoo

A pearly shampoo with Parsol SLX and Phytantriol and the followingingredients can be prepared as follows Ingredients INCI Nomenclature %w/w A Texapon NSO-BZ Sodium Laureth Sulfate 50.00 Carbopol Aqua SF-1Acrylates Copolymer 7.00 Parsol SLX Polysilicone-15 1.00 Kathon CGMethylchloroisothiazolinone 0.10 and Methyl-isothiazolinone D-Panthenol75 L Panthenol 0.50 Deionized Water Aqua 27.40 B NaOH 30% SodiumHydroxide 1.10 C Compound of formula 0.1-25 I or II Cetiol HE PEG-7Glyceryl Cocoate 1.00 Tego Betaine L Cocamidopropyl Betaine 5.00Euperlan PK-3000 OK Glycol Distearate and 3.00 Glycerine and Laureth-4and Cocamidopropyl Betaine EDETA BD Disodium EDTA 0.20 FD&C Blue No.1,CI 42090 0.01 1.0% sol. Natrium Chloride Sodium Chloride 0.50 DCremophor RH 40 PEG-40 Hydrogenated Castor Oil 2.00 PhytantriolPhytantriol 0.20 Perfume Perfume 1.00Procedure: Part A: Add all the ingredients and mix under slow agitation.Neutralize Part A with Part B until a pH of 6.5 is reached. Part C: Addall the ingredients to AB and mix under slow agitation. Mix Part Dtogether, and add it to ABC under moderate agitation.

1. A UV-A screening composition comprising a compound of the generalformula I or II

wherein m is 1 or 2; R¹ and R² are identical or differentelectron-withdrawing groups, or one of R¹ and R² is hydrogen and theother of R¹ and R² is an electron-withdrawing group; R³, R⁴, R⁵, and R⁶are, independently, hydrogen, alkyl, cycloalkyl or aryl; R³ and R⁵and/or R⁴, and R⁶ taken together with the carbon atoms to which they areattached, form a 5 or 6 membered ring which is unsubstituted orsubstituted with one to four alkyl, cycloalkyl or alkoxy groups; X is amoiety R⁷, when m is 1, and is alkylene or poly(oxyalkylene) when m is2; and R⁷ is hydrogen, alkyl, cycloalkyl, alkoxyalkyl or aryl.
 2. Acomposition according to claim 1, wherein the compound of formula I isselected from the group consisting of1-N-(2-ethylhexyl)-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,1-N-dodecyl-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,1-N-[3-(2-ethylhexyloxy)propyl]-4-dicyanomethylene-2,6-dimethyl-1,4-dihydroyridine,1-N-[3,5,5-trimethylhexyl]-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,1-N-methyl-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,1-N-butyl-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine,2-ethylhexyl (1-Butyl-2,6-dimethyl-1H-pyridin-4-ylidene)cyanoacetate,2-{1-[3-(2-{2-[3-(4-dicyanomethylene-2,6-dimethyl-4H-pyridin-1-yl)-propoxy]-ethoxy}-ethoxy)-propyl]-2,6-dimethyl-1H-pyridin-4-ylidene}-malononitrile,and 2-ethylhexyl(1-N-[3-(2-Ethylhexyloxy)propyl]-2,6-dimethyl-1H-pyridin-4-ylidene)cyanoacetate.3. A composition according to claim 1, wherein the compound of formulaII is selected from the group consisting of ethyl(2-6-dimethyl-pyran-4-ylidene) cyanoactate, 2-ethylhexyl(2,6-dimethyl-pyran-4-ylidene)cyanoacetate,2-(2,6-diethyl-3,5-dimethylpyran-4-ylidene)malononitrile and2-(3,5-diethyl-2,6-dipropylpyran-4-ylidene)malononitrile.
 4. Acomposition according to claim 1 comprising from 0.5% by weight to 12%by weight of a compound of formula I or II.
 5. A composition accordingto claim 1 wherein additionally a further UV-A screening agent and/orUV-B screening agent is present.
 6. A composition according to claim 1further comprising a topically applicable, cosmetically acceptablecarrier.
 7. A composition according to claim 1 wherein the compound offormula I or II is incorporated into a plastic substrate.
 8. (Canceled).9. A compound of general formula I or II according to claim 1 wherein R³and R⁴ are alkyl, or wherein R³ and R⁵ and/or R⁴, and R⁶ taken togetherwith the carbon atoms to which they are attached, form a 5 or 6 memberedring which is unsubstituted or substituted with one to four alkyl oralkoxy groups.
 10. A compound of the general formula I according toclaim 1 wherein m is
 2. 11. A compound of the general formula I or IIaccording to claim 1 selected from the group consisting of2-{1-[3-(2-{2-[3-(4-dicyanomethylene-2,6-dimethyl-4H-pyridin-1-yl)-propoxy]-ethoxy}-ethoxy)-propyl]-2,6-dimethyl-1H-pyridin-4-ylidene}-malononitrile;1-N-(2-ethylhexyl)-4-(dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine;1-N-dodecyl-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine;1-N-[3-(2-ethylhexyloxy)propyl]-4-dicyanomethylene-2,6-dimethyl-1,4-dihydroyridine;1-N-[3,5,5-trimethylhexyl]-4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridine;2-ethylhexyl (2,6-dimethyl-pyran-4-ylidene)cyanoacetate; 2-ethylhexyl(1-N-[3-(2-Ethylhexyloxy)propyl]-2,6-dimethyl-1H-pyridin-4-ylidene)cyanoacetate;2-(2,6-diethyl-3,5-dimethylpyran-4-ylidene)malononitrile; and2-(3,5-diethyl-2,6-dipropylpyran-4-ylidene)malononitrile.
 12. Acomposition according to claim 2 comprising from 0.5% by weight to 12%by weight of a compound of formula I.
 13. A composition according toclaim 3 comprising from 0.5% by weight to 12% by weight of a compound offormula II.
 14. A composition according to claim 2 further comprising anadditional UV-A screening agent or UV-B screening agent.
 15. Acomposition according to claim 3 further comprising an additional UV-Ascreening agent or UV-B screening agent.
 16. A composition according toclaim 2 further comprising a topically applicable, cosmeticallyacceptable carrier.
 17. A composition according to claim 3 furthercomprising a topically applicable, cosmetically acceptable carrier. 18.A composition according to claim 2 wherein the compound of formula I orII is incorporated into a plastic substrate.
 19. A composition accordingto claim 3 wherein the compound of formula I or II is incorporated intoa plastic substrate.
 20. A method of protecting a hair or skincomprising applying to a hair or skin a UV-A screening agent comprisinga compound of the general formula I or II:

wherein m is 1 or 2; R¹ and R² are identical or differentelectron-withdrawing groups, or one of R¹ and R² is hydrogen and theother of R¹ and R² is an electron-withdrawing group; R³, R⁴, R⁵, and R⁶are, independently, hydrogen, alkyl, cycloalkyl or aryl; R³ and R⁵and/or R⁴, and R⁶ taken together with the carbon atoms to which they areattached, form a 5 or 6 membered ring which is unsubstituted orsubstituted with one to four alkyl, cycloalkyl or alkoxy groups; X is amoiety R⁷, when m is 1, and is alkylene or poly(oxyalkylene) when m is2; and R⁷ is hydrogen, alkyl, cycloalkyl, alkoxyalkyl or aryl.